CN110546188A

CN110546188A - resin composition, prepreg, resin sheet, metal foil-clad laminate, printed wiring board, and method for producing resin composition

Info

Publication number: CN110546188A
Application number: CN201880026946.1A
Authority: CN
Inventors: 古田亚衣子; 大西展义; 田所弘晃; 山口翔平; 高桥博史; 河合英利
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2017-05-26
Filing date: 2018-05-21
Publication date: 2019-12-06
Anticipated expiration: 2038-05-21
Also published as: JP7116927B2; TW201903058A; TWI769258B; WO2018216647A1; JPWO2018216647A1; KR102494799B1; KR20200013632A; CN110546188B

Abstract

A resin composition comprising an aromatic compound (A) and a maleimide compound (B), wherein the aromatic compound (A) is formed by directly bonding a 1-valent substituent represented by the following formula (1a) and a 1-valent substituent represented by the following formula (1B) to an aromatic ring. CH2 ═ CRaCH2- (1a) RbO- (1b) (in formula (1a), Ra represents a hydrogen atom or a 1-valent organic group, and in formula (1b), Rb represents a 1-valent organic group).

Description

Resin composition, prepreg, resin sheet, metal foil-clad laminate, printed wiring board, and method for producing resin composition

Technical Field

The present invention relates to a resin composition, a prepreg, a resin sheet, a metal foil-clad laminate, a printed wiring board, and a method for producing a resin composition.

Background

In recent years, with the progress of higher functionality and smaller size of semiconductor packages widely used in electronic devices, communication devices, personal computers, and the like, high integration and high-density mounting of each member for a semiconductor package have been accelerated in recent years. Accordingly, warpage of the semiconductor plastic package due to a difference in thermal expansion coefficient between the semiconductor element and the printed circuit board for the semiconductor plastic package becomes a problem, and various measures are being sought.

As one of the measures, it has been studied to increase the glass transition temperature (increase the Tg) of a laminate in a printed wiring board by using a diallylbisphenol a and a maleimide compound in combination (for example, see patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. H02-097561

Disclosure of Invention

Problems to be solved by the invention

However, according to the detailed study of the present inventors, the formability of the printed circuit board is insufficient for the above-mentioned conventional techniques. Further, there is room for further improvement in the storage stability of prepregs as a raw material for printed wiring boards. Therefore, further improvements thereof are desired.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin composition, a prepreg, a resin sheet, a metal foil-clad laminate, a printed circuit board, and a method for producing the resin composition, which are excellent in moldability into a printed circuit board and storage stability of the prepreg.

Means for solving the problems

The present inventors have made extensive studies to achieve the above object. As a result, it has been found that the reason why the moldability of the printed circuit board has been improved in the past is that the melt viscosity of the prepreg as a raw material is high, and the flowability of the resin composition contained in the prepreg is not good when the prepreg is laminated and cured. It is also clear that the prepreg has a high melt viscosity and still has room for improvement in storage stability because, in an aromatic compound having an allyl group (which may be substituted) and a phenolic hydroxyl group in an aromatic ring, such as diallyl bisphenol a, the allyl group is likely to react with a maleimide group in a maleimide compound. Further, as a result of further studies, it was found that a resin composition excellent in moldability into a printed wiring board and storage stability of a prepreg can be obtained by finding a method of appropriately inhibiting the reaction between allyl groups and maleimide groups, and the present invention has been completed.

Namely, the present invention is as follows.

[1] A resin composition comprising an aromatic compound (A) and a maleimide compound (B), wherein the aromatic compound (A) is formed by directly bonding a 1-valent substituent represented by the following formula (1a) and a 1-valent substituent represented by the following formula (1B) to an aromatic ring.

CH＝CRCH- (1a)

RO- (1b)

(in the formula (1a), Ra represents a hydrogen atom or a 1-valent organic group, and in the formula (1b), Rb represents a 1-valent organic group.)

[2] The resin composition according to [1], wherein in the aromatic compound (A), a carbon atom in the aromatic ring to which the 1-valent substituent represented by the formula (1a) is bonded and a carbon atom in the aromatic ring to which the 1-valent substituent represented by the formula (1b) is bonded are adjacent to each other.

[3] The resin composition according to [1] or [2], wherein the 1-valent substituent represented by the formula (1b) is any 1-valent substituent represented by the following formulae (2), (3) and (4).

(in the formulae (2), (3) and (4), R1 represents a linear or branched alkyl group having 1 or more carbon atoms or an aryl group which may be substituted.)

[4] The resin composition according to [3], wherein R1 is a substituent represented by the following formula (5).

(in the formula (5), R2 represents a hydrogen atom or a 1-valent organic group.)

[5] The resin composition according to any one of [1] to [4], wherein the aromatic compound (A) comprises a compound represented by the following formula (6).

(in the formula (6), 2R 3 independently represent a hydroxyl group or an optional substituent represented by the following formulae (2), (3) and (4), at least one of which represents an optional substituent represented by the following formulae (2), (3) and (4), R4 represents a single bond, an alkylene group, a phenylene group, a biphenylene group or a naphthylene group, and R5 independently represent a hydrogen atom, an alkyl group, a phenyl group, a biphenyl group or a naphthyl group.)

[6] The resin composition according to any one of [1] to [5], wherein the maleimide compound (B) is at least 1 selected from the group consisting of bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, polytetrahydrofuran-bis (4-maleimidobenzoate), and a maleimide compound represented by the following formula (7).

(in the formula (7), R6 each independently represents a hydrogen atom or a methyl group, and n1 represents an integer of 1 or more.)

[7] The resin composition according to any one of [1] to [6], further comprising at least 1 selected from the group consisting of an epoxy resin, a cyanate ester compound, and an alkenyl-substituted nadimide.

[8] The resin composition according to any one of [1] to [7], further comprising an inorganic filler (C).

[9] The resin composition according to [8], wherein the inorganic filler (C) contains at least 1 selected from the group consisting of silica, alumina and boehmite.

[10] The resin composition according to [8] or [9], wherein the content of the inorganic filler (C) is 30 to 500 parts by mass per 100 parts by mass of the resin solid content.

[11] A prepreg comprising: a substrate, and the resin composition according to any one of [1] to [10] impregnated or coated on the substrate.

[12] A resin sheet comprising: a support and the resin composition according to any one of [1] to [10] applied to the support.

[13] A laminated plate comprising 1 or more laminated layers of at least 1 selected from the group consisting of the prepreg according to [11] and the resin sheet according to [12], wherein the laminated plate comprises a cured product of a resin composition contained in at least 1 selected from the group consisting of the prepreg and the resin sheet.

[14] A metal-clad laminate comprising: at least 1 selected from the group consisting of the prepreg according to [11] and the resin sheet according to [12], and a metal foil disposed on one surface or both surfaces of at least 1 selected from the group consisting of the prepreg and the resin sheet, wherein the metal foil-clad laminate comprises a cured product of a resin composition contained in at least 1 selected from the group consisting of the prepreg and the resin sheet.

[15] A printed circuit board, comprising: an insulating layer and a conductor layer formed on a surface of the insulating layer, wherein the insulating layer contains the resin composition according to any one of [1] to [10 ].

[16] A method for producing a resin composition, comprising the steps of:

A step in which an aromatic compound (A1) in which a 1-valent substituent represented by the following formula (1a) and a phenolic hydroxyl group are directly bonded to an aromatic ring is reacted with a compound that reacts with the phenolic hydroxyl group to obtain an aromatic compound (A) in which a 1-valent substituent represented by the following formula (1a) and a 1-valent substituent represented by the following formula (1b) are directly bonded to an aromatic ring; and a step of blending the aromatic compound (A) and the maleimide compound (B).

CH＝CRCH- (1a)

RO- (1b)

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a resin composition, a prepreg, a resin sheet, a metal foil-clad laminate, a printed wiring board, and a method for producing a resin composition, which are excellent in moldability into a printed wiring board and storage stability of the prepreg, can be provided.

Detailed Description

Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail, but the present invention is not limited to the present embodiment described below. The present invention can be variously modified within a range not departing from the gist thereof.

(resin composition)

The resin composition of the present embodiment includes an aromatic compound (a) in which a 1-valent substituent represented by the following formula (1a) (hereinafter, referred to as "substituted allyl") and a 1-valent substituent represented by the following formula (1B) (hereinafter, referred to as "substituted hydroxyl") are directly bonded to an aromatic ring, and a maleimide compound (B). Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable.

CH＝CRCH- (1a)

RO- (1b)

In the formula (1a), Ra represents a hydrogen atom or a 1-valent organic group, and the number of carbon atoms in the case of having a carbon atom is preferably 1 to 60. Ra is more preferably a hydrogen atom, an alkyl group or an aryl group having 1 to 60 carbon atoms, still more preferably a hydrogen atom, an alkyl group or an aryl group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom. In the formula (1b), Rb represents a 1-valent organic group, and the carbon number thereof is preferably 3 to 60. The number of carbon atoms of Rb is more preferably 3 to 45, and still more preferably 4 to 43.

In the resin composition, the aromatic compound (a) has a substituted hydroxyl group which is sterically hindered from the substituted allyl group as compared with the phenolic hydroxyl group. Therefore, the progress of the reaction between the substituted allyl group and the maleimide group in the maleimide compound is moderately hindered by the substituted hydroxyl group. Thus, the melt viscosity of the prepreg using the resin composition of the present embodiment can be lower than that of the above-described conventional art. As a result, when the prepreg is laminated and cured, the flowability of the resin composition is improved, and the moldability of the laminate, the metal foil-clad laminate and the printed circuit board is excellent. Further, by appropriately inhibiting the progress of the reaction, the viscosity of the prepreg is also inhibited from increasing with time, and the prepreg is also excellent in storage stability. However, the factors that can be considered are not limited thereto.

(aromatic Compound (A))

The aromatic compound (a) of the present embodiment is one in which a substituted allyl group and a substituted hydroxyl group are directly bonded to an aromatic ring. The substituted hydroxyl group is preferably one having a hydroxyl group, and more preferably one represented by the following formula (1 c).

R-CH(OH)-CH- (1c)

Here, Rc represents a linear or branched alkyl group or aryl group having 1 or more carbon atoms, which may have a substituent or may have oxygen in the chain. The number of carbons of the alkyl group is preferably 4 to 14, and the number of carbons of the aryl group is preferably 6 to 12.

More specifically, the substituted hydroxyl group may be any of the 1-valent substituents represented by the following formulae (2), (3) and (4). From the viewpoint of more effectively and reliably exhibiting the effects of the present invention, an optional substituent having a valence of 1 represented by the following formulae (2), (3) and (4) is preferable.

In the formulae (2), (3) and (4), R1 represents an optionally substituted, straight-chain or branched alkyl group or aryl group having 1 or more carbon atoms. The number of carbons of the alkyl group is preferably 4 to 12, and the number of carbons of the aryl group is preferably 6 to 12. Among these, from the viewpoint of more effectively and reliably exerting the effect of the present invention, an optionally substituted aryl group is preferable, an optionally substituted phenyl group, a biphenyl group or a naphthyl group is more preferable, and an optionally substituted phenyl group represented by the following formula (5) is further preferable.

In formula (5), R2 represents a hydrogen atom or a 1-valent organic group, and when it is a 1-valent organic group, the number of carbon atoms is 1 or more.

Examples of the substituent in R1 include a 1-valent organic group. More specifically, the 1-valent organic group and the 1-valent organic group in R2 include a 1-valent saturated or unsaturated linear or branched hydrocarbon group having 1 to 40 carbon atoms which may be substituted, a 1-valent saturated or unsaturated alicyclic hydrocarbon group having 1 to 40 carbon atoms which may be substituted, and a 1-valent aromatic hydrocarbon group having 1 to 40 carbon atoms which may be substituted. These hydrocarbon groups may have 1 atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom. Examples of the optionally substituted 1-valent saturated or unsaturated linear or branched hydrocarbon group having 1 to 40 carbon atoms include alkyl groups having 1 to 40 carbon atoms represented by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and decyl groups, alkoxy groups having 1 to 40 carbon atoms represented by methoxy, ethoxy and 3-methylmethoxy groups, and vinyl groups. Examples of the optionally substituted saturated or unsaturated alicyclic hydrocarbon group having a valence of 1 to 40 carbon atoms include cyclopropyl, 2-dimethylcyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, menthyl (menthyl group), and cyclododecyl. Examples of the optionally substituted 1-valent aromatic hydrocarbon group having 1 to 40 carbon atoms include an optionally substituted phenyl group represented by a 4- (tert-butyl) phenyl group, a 2-methylphenyl group, a 4-methylphenyl group and a 4-methoxyphenyl group, and an optionally substituted phenoxy group represented by a phenoxy group. In addition, from the viewpoint of more effectively and reliably exhibiting the effects of the present invention, the number of carbon atoms in each hydrocarbon group is preferably 3 to 20. When R2 is a 1-valent organic group, the carbon number is preferably 1 to 9. Examples of the 1-valent organic group include those having 1 to 9 carbon atoms among the groups exemplified above.

More specifically, the aromatic compound (a) includes a compound represented by the following formula (6). This compound is preferable from the viewpoint of more effectively and reliably exhibiting the effect of the present invention. The aromatic compound (a) may be used alone in 1 kind or in combination of 2 or more kinds.

In formula (6), 2R 3 each independently represents a hydroxyl group or an optional substituent represented by formula (2), (3) or (4) above, and at least one of R3 represents an optional substituent represented by formula (2), (3) or (4) above, R4 represents a single bond, an alkylene group, a phenylene group, a biphenylene group or a naphthylene group, and R5 each independently represents a hydrogen atom, an alkyl group, a phenyl group, a biphenyl group or a naphthyl group. Examples of the alkyl group in R5 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a decyl group. Further, R4 includes, for example, a 2-valent group in which 2 aromatic rings in bisphenol a, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z are bonded. Among these, R4 is preferably an isopropylidene (> C (CH3)2) group having 2 valences to bond 2 aromatic rings in bisphenol a.

In the aromatic compound (a) of the present embodiment, it is preferable that the carbon atom in the aromatic ring to which the substituted allyl group is bonded and the carbon atom in the aromatic ring to which the substituted hydroxyl group is bonded are adjacent to each other. This can more appropriately suppress the progress of the reaction between the substituted allyl group in the aromatic compound (a) and the maleimide group in the maleimide compound (B). As a result, the resin composition of the present embodiment is more excellent in moldability into a printed circuit board and storage stability of a prepreg.

The aromatic compound (a) can be produced by a conventional method, or can be obtained as a commercially available product. Examples of the method for producing the aromatic compound (a) include a step of obtaining the aromatic compound (a) in the method for producing the resin composition of the present embodiment, which will be described later, and production methods described in examples.

In the resin composition of the present embodiment, the content of the aromatic compound (a) is preferably 5 parts by mass or more and 50 parts by mass or less, and more preferably 8 parts by mass or more and 30 parts by mass or less, with respect to 100 parts by mass of the resin solid content. When the content of the aromatic compound (a) is in the above range, the moldability of the printed circuit board and the storage stability of the prepreg are further excellent. In the present embodiment, the term "resin solid content" refers to components other than the solvent and the filler in the resin composition unless otherwise specified, and "100 parts by mass of the resin solid content" refers to 100 parts by mass of the total of the components other than the solvent and the filler in the resin composition.

(Maleimide Compound (B))

The maleimide compound (B) of the present embodiment is not particularly limited as long as it is a compound having 1 or more maleimide groups in the molecule. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, a maleimide compound represented by the following formula (7), a prepolymer of these maleimide compounds, or a prepolymer of a maleimide compound and an amine compound. These may be used in 1 kind or in a suitable mixture of 2 or more kinds.

Among them, bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and a maleimide compound represented by the following formula (7) are preferable, and a maleimide compound represented by the following formula (7) is particularly preferable. By containing such a maleimide compound, the resulting cured product tends to have more excellent heat resistance and elastic modulus retention rate.

In formula (7), R6 each independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. In the formula, n1 represents an integer of 1 or more. The upper limit value of n1 is preferably 10, more preferably 7.

In the resin composition of the present embodiment, the content of the maleimide compound (B) is preferably 5 parts by mass or more and 70 parts by mass or less, and more preferably 10 parts by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the resin solid content. When the content of the maleimide compound (B) is in the above range, the moldability into a printed circuit board and the storage stability of the prepreg are further excellent, and the thermal expansion coefficient of the obtained cured product tends to be further reduced and the heat resistance tends to be further improved.

In the resin composition of the present embodiment, when the compound having an alkenyl group contained therein is only the aromatic compound (a), the ratio ((β)/(α)) of the number of alkenyl groups (α) in the aromatic compound (a) to the number of maleimide groups (β) in the maleimide compound (B) is preferably 0.9 to 4.3, more preferably 1.5 to 4.0. By setting the ratio ((β)/(α)) within the above range, the moldability of the printed wiring board and the storage stability of the prepreg become better, and a printed wiring board having excellent low thermal expansion, thermal elastic modulus, heat resistance, moisture absorption heat resistance, desmear resistance, chemical resistance, and easy curability can be obtained.

(optional Components)

The resin composition of the present embodiment preferably further includes at least 1 selected from the group consisting of an epoxy resin, a cyanate ester compound, and an alkenyl-substituted nadimide. Among these, the resin composition of the present embodiment more preferably contains an alkenyl-substituted nadimide from the viewpoint of more effectively and reliably exhibiting the effects of the present invention.

The alkenyl-substituted nadimide according to the present embodiment is not particularly limited as long as it is a compound having 1 or more alkenyl-substituted nadimide groups in a molecule. Specific examples thereof include compounds represented by the following formula (8).

In the formula (8), R7 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R8 represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by the following formula (9) or (10).

In formula (9), R9 represents a substituent represented by a methylene group, an isopropylidene group, CO, O, S, or SO 2.

In the formula (10), R10 represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms, each independently selected.

Further, a commercially available alkenyl-substituted nadimide represented by the formula (8) may be used. The commercially available substance is not particularly limited, and examples thereof include a compound represented by the following formula (11) (BANI-M (manufactured by PELLE PETROL CO., LTD.)) and a compound represented by the following formula (12) (BANI-X (manufactured by PELLE PETROL Chemicals Co., LTD.)). These may be used in 1 kind or in combination of 2 or more kinds.

In the resin composition of the present embodiment, the content of the alkenyl-substituted nadimide is preferably 10 to 60 parts by mass, more preferably 20 to 40 parts by mass, per 100 parts by mass of the resin solid content. By setting the content of the alkenyl-substituted nadimide within such a range, moldability is also excellent when the inorganic filler is filled. Further, a printed wiring board excellent in curability, for example, a thermal elastic modulus such as a flexural modulus at 250 ℃ and a flexural modulus at a reflow soldering temperature, desmear resistance, and chemical resistance can be obtained. However, from the viewpoint of further improving the moldability of the printed wiring board, it is preferable that the resin composition does not contain an alkenyl-substituted nadimide.

In addition, when the resin composition of the present embodiment contains an optional component having an alkenyl group such as an alkenyl-substituted nadimide in addition to the aromatic compound (a), the ratio ((β)/(α t)) of the total number of alkenyl groups (α t) of the components in the resin composition to the number of maleimide groups (β) in the maleimide compound (B) is preferably 0.9 to 4.3, and more preferably 1.5 to 4.0. By setting the ratio ((β)/(α t)) within the above range, the moldability of the printed wiring board and the storage stability of the prepreg become better, and a printed wiring board having excellent low thermal expansion, thermal elastic modulus, heat resistance, moisture absorption heat resistance, desmear resistance, chemical resistance, and easy curability can be obtained.

(cyanate ester compound)

The resin composition of the present embodiment may further contain a cyanate ester compound. The cyanate ester compound is not particularly limited, and examples thereof include naphthol aralkyl type cyanate ester represented by the following formula (13), novolak type cyanate ester represented by the following formula (14), biphenyl aralkyl type cyanate ester, bis (3, 5-dimethyl 4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1, 3-dicyanobenzene, 1, 4-dicyanobenzene, 1,3, 5-tricyanobenzene, 1, 3-dicyanobenzene, 1, 4-dicyanobenzene, 1, 6-dicyanobenzene, 1, 8-dicyanobenzene, 2, 6-dicyanobenzene, 2, 7-dicyanobenzene, 1,3, 6-tricyanobenzene, 4' -dicyanobenzene, bis (4-cyanatophenyl) ether, and bis (4-dicyanobenzene) ether, Bis (4-cyanatophenyl) sulfide, bis (4-cyanatophenyl) sulfone, and 2, 2' -bis (4-cyanatophenyl) propane; prepolymers of these cyanate esters. These cyanate ester compounds may be used alone in 1 kind, or in combination with 2 or more kinds.

Here, in formula (13), R11 each independently represents a hydrogen atom or a methyl group, with a hydrogen atom being preferred. In formula (13), n2 represents an integer of 1 or more. The upper limit of n2 is usually 10, preferably 6.

Here, in formula (14), R12 each independently represents a hydrogen atom or a methyl group, with a hydrogen atom being preferred. In formula (14), n3 represents an integer of 1 or more. The upper limit of n3 is usually 10, preferably 7.

Among these, the cyanate ester compound preferably contains 1 or more selected from the group consisting of naphthol aralkyl type cyanate ester represented by formula (13), novolac type cyanate ester represented by formula (14), and biphenyl aralkyl type cyanate ester, and more preferably contains 1 or more selected from the group consisting of naphthol aralkyl type cyanate ester represented by formula (13) and novolac type cyanate ester represented by formula (14). By using such a cyanate ester compound, a cured product having excellent flame retardancy, higher curability, and a lower thermal expansion coefficient tends to be obtained.

The method for producing these cyanate ester compounds is not particularly limited, and a known method for synthesizing a cyanate ester compound can be used. The known method is not particularly limited, and examples thereof include the following: a method of reacting a phenol resin with a cyanogen halide in an inactive organic solvent in the presence of a basic compound; a method comprising forming a salt of a phenol resin and an alkaline compound in a solution containing water and subjecting the resulting salt to 2-phase interfacial reaction with a cyanogen halide.

the phenolic resin as a raw material of these cyanate ester compounds is not particularly limited, and examples thereof include naphthol aralkyl type phenolic resins, novolac type phenolic resins, and biphenyl aralkyl type phenolic resins represented by the following formula (15).

here, in formula (15), R11 each independently represents a hydrogen atom or a methyl group, with a hydrogen atom being preferred. In formula (15), n4 represents an integer of 1 or more. The upper limit of n4 is usually 10, preferably 6.

The naphthol aralkyl type phenol resin represented by the formula (15) can be obtained by condensing a naphthol aralkyl resin with cyanic acid. The naphthol aralkyl type phenol resin is not particularly limited, and examples thereof include those obtained by reacting a naphthol such as α -naphthol or β -naphthol with a benzene such as p-xylylene glycol, α' -dimethoxy-p-xylene, or 1, 4-bis (2-hydroxy-2-propyl) benzene. The naphthol aralkyl type cyanate ester may be selected from those obtained by condensing a naphthol aralkyl resin with cyanic acid as described above.

the content of the cyanate ester compound is preferably 0.5 to 45 parts by mass, and more preferably 5 to 20 parts by mass, per 100 parts by mass of the resin solid content. When the content of the cyanate ester compound is in the above range, the heat resistance and chemical resistance of the obtained cured product tend to be further improved.

(epoxy resin)

The resin composition of the present embodiment may further contain an epoxy resin. The epoxy resin is not particularly limited as long as it is a resin having 2 or more epoxy groups in 1 molecule, and for example, examples of the epoxy resin include bisphenol a type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol a novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, 3-functional phenol type epoxy resin, 4-functional phenol type epoxy resin, glycidyl ester type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, aralkyl novolac type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyhydric alcohol type epoxy resin, isocyanurate ring-containing epoxy resin, and halides thereof. Among these, biphenyl aralkyl type epoxy resins are preferred.

The content of the epoxy resin is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass, per 100 parts by mass of the resin solid content. When the content of the epoxy resin is in the above range, flexibility, copper foil peel strength, chemical resistance, and desmear resistance of the obtained cured product tend to be further improved.

(inorganic Filler (C))

The resin composition of the present embodiment may further contain an inorganic filler (C). The inorganic filler (C) is not particularly limited, and examples thereof include silicas such as natural silica, fused silica, synthetic silica, amorphous silica, AEROSIL, and hollow silica; silicon compounds such as white carbon black; metal oxides such as titanium white, zinc oxide, magnesium oxide, and zirconium oxide; metal nitrides such as boron nitride, agglomerated boron nitride, silicon nitride, boehmite, and the like; metal sulfates such as barium sulfate; metal hydrates such as aluminum hydroxide, aluminum hydroxide heat-treated products (products obtained by heat-treating aluminum hydroxide to reduce a part of crystal water), boehmite, and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc compounds such as zinc borate and zinc stannate; alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass short fibers (including glass fine powders such as E glass, T glass, D glass, S glass, Q glass), hollow glass, and spherical glass. The inorganic filler (C) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Among them, the inorganic filler (C) preferably contains at least 1 selected from the group consisting of silica, alumina, magnesia, aluminum hydroxide, boehmite, boron nitride, aggregated boron nitride, silicon nitride, and boehmite, and more preferably contains at least 1 selected from the group consisting of silica, alumina, and boehmite. By using such an inorganic filler (C), the cured product obtained tends to have higher rigidity and lower warpage.

The content of the inorganic filler (C) is preferably 30 to 500 parts by mass, more preferably 100 to 400 parts by mass, and still more preferably 150 to 300 parts by mass, per 100 parts by mass of the resin solid content. When the content of the inorganic filler (C) is in the above range, the rigidity and warpage of the obtained cured product tend to be further increased.

(silane coupling agent and wetting dispersant)

The resin composition of the present embodiment may further contain 1 or more selected from the group consisting of a silane coupling agent and a wetting dispersant. When the resin composition contains the silane coupling agent and the wetting dispersant, the dispersibility of the inorganic filler (C), the resin component, the inorganic filler (C), and the adhesive strength of the substrate described later tend to be further improved.

The silane coupling agent is not particularly limited as long as it is a silane coupling agent used for surface treatment of a general inorganic substance, and examples thereof include aminosilane compounds such as γ -aminopropyltriethoxysilane and N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane; epoxy silane compounds such as gamma-glycidoxypropyltrimethoxysilane; acrylic silane compounds such as gamma-acryloxypropyltrimethoxysilane; cationic silane compounds such as N-beta- (N-vinylbenzylaminoethyl) -gamma-aminopropyltrimethoxysilane hydrochloride; and a phenylsilane-based compound. The silane coupling agent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The wetting dispersant is not particularly limited as long as it is a dispersion stabilizer used for coating materials, and examples thereof include DISPERBYK-110, 111, 118, 180, 161, BYK-W996, W9010 and W903 manufactured by BYK Japan KK.

(other resins, etc.)

The resin composition of the present embodiment may further contain 1 or 2 or more selected from the group consisting of a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group, as necessary. When the resin composition contains such another resin or the like, the peel strength, flexural modulus, and the like of the copper foil of the obtained cured product tend to be further improved.

(phenol resin)

As the phenol resin, a generally known phenol resin can be used as long as it has 2 or more hydroxyl groups in 1 molecule, and the type thereof is not particularly limited. Specific examples thereof include bisphenol a type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol a novolac type phenol resin, glycidyl ester type phenol resin, aralkyl type phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, multifunctional phenol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton-modified novolac type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic type phenol resin, polyhydric alcohol type phenol resin, phosphorus-containing phenol resin, and hydroxyl group-containing silicone resin, and are not particularly limited. These phenol resin can be used alone in 1 or a combination of 2 or more. When the resin composition contains such a phenol resin, the resulting cured product tends to have more excellent adhesiveness, flexibility, and the like.

The content of the phenolic resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 parts by mass, per 100 parts by mass of the resin solid content. When the content of the phenol resin is in the above range, the obtained cured product tends to have further excellent adhesiveness, flexibility, and the like.

(Oxetane resin)

As the oxetane resin, a generally known one can be used, and the kind thereof is not particularly limited. Specific examples thereof include alkyloxetanes such as oxetane, 2-methyloxetane, 2-dimethyloxetane, 3-methyloxetane and 3, 3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3' -bis (trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane, 3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (trade name manufactured by Toyo Seiya Synthesis), and OXT-121 (trade name manufactured by Toyo Seiya Synthesis). These oxetane resins can be used in 1 kind or in combination of 2 or more kinds. When the resin composition contains such an oxetane resin, the resulting cured product tends to have more excellent adhesiveness, flexibility, and the like.

The content of the oxetane resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 parts by mass, per 100 parts by mass of the resin solid content. When the content of the oxetane resin is in the above range, the obtained cured product tends to have more excellent adhesion, flexibility, and the like.

(benzoxazine compound)

As the benzoxazine compound, a generally known compound can be used as long as it has 2 or more dihydrobenzoxazine rings in 1 molecule, and the kind thereof is not particularly limited. Specific examples thereof include bisphenol A type benzoxazine BA-BXZ (trade name of Seikagaku corporation), bisphenol F type benzoxazine BF-BXZ (trade name of Seikagaku corporation), and bisphenol S type benzoxazine BS-BXZ (trade name of Seikagaku corporation). These benzoxazine compounds may be used in 1 kind or in a mixture of 2 or more kinds. When the resin composition contains such a benzoxazine compound, the cured product obtained tends to be more excellent in flame retardancy, heat resistance, low water absorption, low dielectric characteristics, and the like.

The content of the benzoxazine compound is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 parts by mass, based on 100 parts by mass of the resin solid content. When the content of the benzoxazine compound is in the above range, the heat resistance and the like of the obtained cured product tend to be further excellent.

(Compound having polymerizable unsaturated group)

As the compound having a polymerizable unsaturated group, a generally known compound can be used, and the kind thereof is not particularly limited. Specific examples thereof include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene and divinylbiphenyl; (meth) acrylates of 1-or polyhydric alcohols such as methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.; epoxy (meth) acrylates such as bisphenol a epoxy (meth) acrylate and bisphenol F epoxy (meth) acrylate; and benzocyclobutene resins. These compounds having an unsaturated group may be used in 1 kind or in a mixture of 2 or more kinds. When the resin composition contains such a compound having a polymerizable unsaturated group, the resulting cured product tends to have more excellent heat resistance, toughness, and the like.

The content of the compound having a polymerizable unsaturated group is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 parts by mass, based on 100 parts by mass of the resin solid content. When the content of the compound having a polymerizable unsaturated group is in the above range, the resultant cured product tends to have further excellent heat resistance, toughness, and the like.

(curing accelerators)

The resin composition of the present embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include imidazoles such as triphenylimidazole; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, di-tert-butyl diperoxyphthalate, etc.; azo compounds such as azobisnitrile; tertiary amines such as N, N-dimethylbenzylamine, N-dimethylaniline, N-dimethyltoluidine, N-lutidine, 2-N-ethylanilinoethanol, tri-N-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, catechol, and the like; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate, and the like; the organic metal salts are dissolved in a hydroxyl group-containing compound such as phenol or bisphenol; inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; and organotin compounds such as dioctyltin oxide, other alkyltin oxides, and alkyltin oxides. Of these, triphenylimidazole is particularly preferable because it tends to promote the curing reaction and is excellent in glass transition temperature and thermal expansion coefficient.

(solvent)

The resin composition of the present embodiment may further contain a solvent. When the resin composition contains a solvent, the viscosity during the production of the resin composition is reduced, the handling property is further improved, and the impregnation property into a base material described later tends to be further improved.

The solvent is not particularly limited as long as it can dissolve a part or all of the resin components in the resin composition, and examples thereof include ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; and propylene glycol monomethyl ether and its acetate. The solvent may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

(method for producing resin composition)

The method for producing the resin composition of the present embodiment is not particularly limited, and includes, for example, the following steps: a step in which an aromatic compound (A1) in which a substituted allyl group and a phenolic hydroxyl group are directly bonded to an aromatic ring is reacted with a compound that reacts with the phenolic hydroxyl group to obtain an aromatic compound (A) in which a substituted allyl group and a substituted hydroxyl group are directly bonded to an aromatic ring; and a step of blending the aromatic compound (A) and the maleimide compound (B).

The aromatic compound (a1) is formed by bonding a substituted allyl group and a phenolic hydroxyl group directly to an aromatic ring. Such an aromatic compound (a1) is not particularly limited, and examples thereof include compounds represented by the following formula (16).

In formula (16), R4 and R5 are as defined above for formula (6).

Examples of the compound that reacts with a phenolic hydroxyl group include monofunctional epoxy compounds. Examples of the monofunctional epoxy compound include any of the compounds represented by the following formulae (17), (18) and (19), and these compounds are preferable from the viewpoint of more effectively and reliably exhibiting the effects of the present invention.

Here, in the formulae (17), (18) and (19), R1 is the same as in the formulae (2), (3) and (4). From the viewpoint of more effectively and reliably exerting the effect of the present invention, R1 is preferably an optionally substituted aryl group, more preferably an optionally substituted phenyl, biphenyl or naphthyl group, and preferably an optionally substituted phenyl group represented by the above formula (5).

In the aromatic compound (a1) according to the present embodiment, it is preferable that the carbon atom in the aromatic ring bonded to the substituted allyl group and the carbon atom in the aromatic ring bonded to the phenolic hydroxyl group are adjacent to each other. This can more appropriately suppress the progress of the reaction between the substituted allyl group in the aromatic compound (a) and the maleimide group in the maleimide compound (B). As a result, the resin composition of the present embodiment is more excellent in moldability into a printed circuit board and storage stability of a prepreg.

If necessary, a curing accelerator may be added in the step of obtaining the aromatic compound (a). Examples of the curing accelerator include those described above. The amount of the curing accelerator to be added is not particularly limited as long as the aromatic compound (a) can be obtained, and is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the aromatic compound (a) to be obtained.

The reaction temperature in the step of obtaining the aromatic compound (a) is not particularly limited as long as the aromatic compound (a) can be obtained, and is preferably 50 ℃ or more and 160 ℃ or less, more preferably 100 ℃ or more and 140 ℃ or less.

Next, the aromatic compound (a) and the maleimide compound (B) are compounded. In this step, the aromatic compound (a), the maleimide compound (B), and other components contained in the resin composition are sequentially mixed with a solvent and sufficiently stirred to obtain the resin composition. In this case, known processes such as stirring, mixing, and kneading may be performed to uniformly dissolve or disperse the respective components. Specifically, the dispersibility of the inorganic filler (C) in the resin composition can be improved by performing the stirring dispersion treatment using a stirring tank equipped with a stirrer having an appropriate stirring capability. The stirring, mixing and kneading processes can be suitably carried out by using a known apparatus such as an apparatus for mixing purposes, e.g., a ball mill or a bead mill, or a revolution or rotation type mixing apparatus.

In addition, in the preparation of the resin composition of the present embodiment, an organic solvent and/or a curing accelerator may be used as necessary. The type of the organic solvent is not particularly limited as long as the resin in the resin composition can be dissolved therein. Specific examples thereof are as described above. The type of the curing accelerator is not particularly limited as long as it accelerates the curing of the resin composition. Specific examples thereof are as described above.

(use)

(prepreg)

The prepreg of the present embodiment is a prepreg including a substrate and the resin composition impregnated or coated on the substrate. The prepreg production method can be carried out by a conventional method, and is not particularly limited. For example, the prepreg of the present embodiment may be produced by impregnating or applying the resin component of the present embodiment to a substrate, and then semi-curing (B-staging) the impregnated or applied resin component by heating the resin component in a dryer at 100 to 200 ℃ for 1 to 30 minutes.

The content of the resin composition (including the inorganic filler) is not particularly limited, and is preferably 30 to 90 mass%, more preferably 35 to 85 mass%, and still more preferably 40 to 80 mass% with respect to the total mass of the prepreg. When the content of the resin composition is within the above range, moldability tends to be further improved. From the same viewpoint, the content of the base material is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, and still more preferably 20 to 60% by mass, based on the total mass of the prepreg.

The substrate is not particularly limited, and known substrates used for various printed wiring board materials can be suitably selected and used in accordance with the intended use and performance. Specific examples thereof are not particularly limited, and include, for example, glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, and T glass; inorganic fibers other than glass such as quartz; wholly aromatic polyamides such as poly (paraphenylene terephthalamide) (Kevlar (registered trademark), manufactured by Du Pont), copoly (p-phenylene 3, 4' -oxydiphenylene-p-phenylenediamine) (Technora (registered trademark), manufactured by Teijin Techno Products limited); polyesters such as 2, 6-hydroxynaphthoic acid-p-hydroxybenzoic acid (Vectran (registered trademark), KURARAY co., LTD), and Zxion (registered trademark, KB SEIREN, LTD); and organic fibers such as polyparaphenylene benzoxazole (Zylon (registered trademark), available from Toyo Boseki Co., Ltd.) and polyimide. Among these, E glass, T glass, S glass, Q glass, and organic fiber are preferable from the viewpoint of low thermal expansion coefficient. These substrates may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The shape of the substrate is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat. The weaving method of the woven fabric is not particularly limited, and for example, plain weave, herringbone weave, twill weave, and the like are known, and can be appropriately selected from these known weaving methods according to the intended use and performance. Further, a glass woven fabric obtained by subjecting these to a fiber-opening treatment or a surface treatment with a silane compound such as a silane coupling agent can be suitably used. The thickness and mass of the substrate are not particularly limited, and a substrate having a thickness of about 0.01 to 0.3mm can be suitably used in general. In particular, from the viewpoint of strength and water absorption, the substrate is preferably a glass woven fabric having a thickness of 200 μm or less and a mass (basis weight) of 250g/m2 or less, and more preferably a woven fabric (cloth) of 1 or more kinds of fibers selected from the group consisting of glass fibers of E glass, S glass, T glass, and Q glass and organic fibers.

The prepreg of the present embodiment includes the resin composition described above, and thus has excellent storage stability. This is considered to be because the progress of the reaction between the substituted allyl group in the aromatic compound (a) and the maleimide group in the maleimide compound is moderately hindered by the substituent in the aromatic compound (a), and as a result, the viscosity increase of the prepreg with time is suppressed.

(resin sheet)

The resin sheet of the present embodiment includes a support (sheet base) and the resin composition applied to the sheet base, and the resin composition is laminated on one surface or both surfaces of the sheet base. Since the resin sheet is used as 1 means for forming a sheet, it can be produced by directly applying a thermosetting resin (including an inorganic filler) used in a prepreg or the like to a support such as a metal foil or a film and drying the resin.

The sheet base is not particularly limited, and known materials used for various printed circuit board materials can be used. Examples of the sheet base include a polyimide film, a polyamide film, a polyester film, a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a polypropylene (PP) film, a Polyethylene (PE) film, an aluminum foil, a copper foil, and a gold foil. Among them, electrolytic copper foil and PET film are preferable.

Examples of the coating method include a method of coating a sheet base material with a solution obtained by dissolving the resin composition of the present embodiment in a solvent, using a bar coater, a die coater, a squeegee, a baker's applicator, or the like.

the resin sheet is preferably obtained by applying the resin composition to a support (sheet base) and then semi-curing (B-staging). Specific examples of the method for obtaining such a resin sheet include the following: the resin composition is coated on a sheet base material such as a copper foil, and then semi-cured by a method of heating in a drier at 100 to 200 ℃ for 1 to 60 minutes, to produce a resin sheet. The amount of the resin composition attached to the support is preferably in the range of 1 to 300 μm in terms of the resin thickness of the resin sheet. The resin sheet of the present embodiment can be used as a build-up material for a printed circuit board.

(laminate and Metal foil-clad laminate)

The laminate of the present embodiment is obtained by laminating 1 or more sheets of at least 1 kind selected from the group consisting of the prepregs and the resin sheets described above, and includes a cured product of a resin composition contained in at least 1 kind selected from the group consisting of the prepregs and the resin sheets described above. The laminate can be obtained by laminating 1 or more sheets of at least 1 kind selected from the group consisting of the prepreg and the resin sheet and curing the laminate. Further, the metal foil-clad laminate of the present embodiment includes: and a metal foil disposed on one or both surfaces of at least 1 selected from the group consisting of the prepregs and the resin sheets, wherein the metal foil-clad laminate comprises a cured product of a resin composition contained in at least 1 selected from the group consisting of the prepregs and the resin sheets. The metal foil-clad laminate can be obtained by laminating at least 1 kind selected from the group consisting of the prepreg and the resin sheet by 1 sheet or more, and disposing metal foils on one surface or both surfaces thereof. More specifically, a metal foil-clad laminate can be produced by stacking 1 or more sheets of the prepreg and/or the resin sheet, and if desired, arranging a metal foil such as copper or aluminum on one surface or both surfaces of the prepreg and/or the resin sheet, and then laminating and molding the prepreg and/or the resin sheet as necessary. The metal foil used here is not particularly limited as long as it is a metal foil used for a printed wiring board material, and a known copper foil such as a rolled copper foil or an electrolytic copper foil is preferable. The thickness of the metal foil is not particularly limited, but is preferably 1 to 70 μm, more preferably 1.5 to 35 μm. The method and conditions for forming the metal-clad laminate are not particularly limited, and the methods and conditions for forming a laminate and a multilayer board for a printed wiring board can be generally applied. For example, a multi-stage press, a multi-stage vacuum press, a continuous press, an autoclave press, or the like can be used for molding the metal-clad laminate. In the molding of the metal-clad laminate, the temperature is usually 100 to 300 ℃, the pressure is 2 to 100kgf/cm2, and the heating time is usually 0.05 to 5 hours. Further, if necessary, post-curing may be performed at a temperature of 150 to 300 ℃. Further, a multilayer board can also be produced by laminating and molding the prepreg and a separately prepared wiring board for an inner layer.

(printed Circuit Board)

the printed wiring board of the present embodiment includes an insulating layer and a conductor layer formed on a surface of the insulating layer, and the insulating layer includes the resin composition. The conductor layer to be a circuit may be formed of a metal foil in the metal foil-clad laminate. Alternatively, the conductor layer may be formed on the surface of the insulating layer by electroless plating. The printed wiring board is excellent in chemical resistance, desmear resistance and insulation reliability, and can be used effectively as a printed wiring board for a semiconductor package which is required to have such properties.

The printed wiring board of the present embodiment can be manufactured by the following method. First, the above-described metal foil-clad laminate (copper-clad laminate or the like) is prepared. The surface of the metal foil-clad laminate is etched to form an inner layer circuit, thereby producing an inner layer substrate. The inner layer circuit surface of the inner layer substrate is subjected to surface treatment for improving the adhesive strength as required. Then, a desired number of the prepregs are stacked on the surface of the inner layer circuit, and further, a metal foil for the outer layer circuit is stacked on the outer side thereof, and the prepregs are integrally molded by heating and pressing. In this way, a multilayer laminate in which an insulating layer including a base material and a cured product of a thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit is manufactured. Next, the multilayer laminated board is subjected to drilling for via holes and via holes. Thereafter, in order to remove the resin residue, i.e., the smear, derived from the resin component contained in the cured product layer, desmear treatment is performed. Then, a metal plating film for electrically connecting the inner layer circuit and the metal foil for the outer layer circuit is formed on the hole wall surface, and the metal foil for the outer layer circuit is etched to form the outer layer circuit, thereby manufacturing a printed wiring board.

For example, the prepreg (the base material and the resin composition attached thereto) and the resin composition layer (the layer formed of the resin composition) of the metal foil-clad laminate constitute an insulating layer containing the resin composition.

In addition, in the case where a metal foil-clad laminate is not used, a conductor layer serving as a circuit may be formed on the prepreg or the resin sheet to produce a printed wiring board. In this case, the conductor layer may be formed by electroless plating.

According to the present embodiment, the progress of the reaction between the substituted allyl group in the aromatic compound (a) and the maleimide group in the maleimide compound is moderately hindered by the substituent group in the aromatic compound (a). As a result, the prepreg has a lower melt viscosity than that of the prior art, and therefore, when the prepreg is laminated and cured, the flowability of the resin composition is improved, and the moldability of the printed circuit board is excellent.

Examples

the present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

(Synthesis example 1) Synthesis of α -Naphthol aralkyl type cyanate ester resin

An α -naphthol aralkyl type phenol resin (SN495V, OH group equivalent: 236g/eq., Nippon iron chemical Co., Ltd.) 300g (1.28 mol in terms of OH group) and triethylamine 194.6g (1.92 mol; 1.5mol based on 1mol of a hydroxyl group) were dissolved in 1800g of methylene chloride to prepare solution 1. For cyanogen chloride 125.9g (2.05 mol; 1.6mol based on hydroxyl group), methylene chloride 293.8g, 36% hydrochloric acid 194.5g (1.92 mol; 1.5mol based on hydroxyl group), and water 1205.9g, solution 1 was added dropwise over 30 minutes while maintaining the solution temperature at-2 ℃ to-0.5 ℃ under stirring. After completion of the dropwise addition of the solution 1, the mixture was stirred at the same temperature for 30 minutes, and then a solution (solution 2) prepared by dissolving 65g (0.64 mol; 0.5mol based on 1mol of the hydroxyl group) of triethylamine in 65g of methylene chloride was added dropwise over 10 minutes. After the completion of the dropwise addition of the solution 2, the reaction was terminated by stirring at the same temperature for 30 minutes. Thereafter, the reaction solution was allowed to stand to separate an organic phase and an aqueous phase. The organic phase obtained is washed 5 times with 1300g of water. The conductivity of the wastewater of the 5 th water washing was 5. mu.S/cm, and it was confirmed that the ionic compounds to be removed were sufficiently removed by the washing with water. The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated and dried at 90 ℃ for 1 hour to obtain 331g of a naphthol aralkyl type cyanate ester compound represented by the above formula (13) (wherein R11 are all hydrogen atoms. SN495V-CN, cyanate equivalent: 261g/eq., orange viscous substance). The obtained infrared absorption spectrum of SN495V-CN showed an absorption of 2250cm-1 (cyanate group) and showed no absorption of a hydroxyl group.

Synthesis example 2 Synthesis of aromatic Compound (A)

In the reactor, 5.0 parts by mass of diallylbisphenol A (DABPA, manufactured by Daohuako chemical industries, Ltd., hydroxyl equivalent: 154g/eq.) corresponding to the aromatic compound (A1), 7.5 parts by mass of a monofunctional epoxy compound (product name "ED-509E", manufactured by ADEKA Co., Ltd.) corresponding to the compound that reacts with the phenolic hydroxyl group, and 0.05 parts by mass of an imidazole-based curing accelerator (2,4, 5-triphenylimidazole, manufactured by Tokyo chemical industries, Ltd.)) were mixed. The mixture was heated at 135 ℃ for 1 hour or more until the reaction was completed, whereby a compound represented by the following formula (21) corresponding to the aromatic compound (A) was obtained. The completion of the reaction was confirmed by GPC (gel permeation chromatography).

(Synthesis example 3) Synthesis of aromatic Compound

In a reactor, 5.3 parts by mass of diallylbisphenol A (DABPA, manufactured by Daohuazai Kaisha, hydroxyl equivalent: 154g/eq.) corresponding to the aromatic compound (A1), 7.1 parts by mass of a monofunctional epoxy compound (product name "YED-188", manufactured by Mitsubishi chemical corporation) and 0.05 part by mass of an imidazole-based curing accelerator (2,4, 5-triphenylimidazole, manufactured by Tokyo Kaisha) were mixed. The mixture was heated at 135 ℃ for 1 hour or more until the reaction was completed, whereby a compound represented by the following formula (22) corresponding to the aromatic compound (A) was obtained. Completion of the reaction was confirmed by GPC (gel permeation chromatography).

(example 1)

10.0 parts by mass of the α -naphthol aralkyl type cyanate ester resin obtained in Synthesis example 1, 45.0 parts by mass of a novolak type maleimide compound (BMI-2300, manufactured by Dahe chemical Co., Ltd., functional group equivalent: 186g/eq.), 25.0 parts by mass of diallyl nanodiscmide (BANI-M, manufactured by Takayasu petrochemical Co., Ltd., functional group equivalent: 286g/eq.), 12.5 parts by mass of the compound represented by the above formula (21) obtained in Synthesis example 2, 6.9 parts by mass of a biphenyl aralkyl type epoxy compound (NC-3000H, manufactured by Nippon chemical Co., Ltd., functional group equivalent: 290g/eq.), 6.0 parts by mass of a silane coupling agent (Z-6040, Dow Corning Co., Ltd.), 6.9 parts by mass of a wetting dispersant (DISPERBYK-111, manufactured by Japan K Japan) and 1.0 part by YKK. and 1.0 part by mass of a wetting dispersant (DISK-161. YKK), BYK Japan KK) 1.0 part by mass, an imidazole curing accelerator (2,4, 5-triphenylimidazole (manufactured by tokyo chemical industry co.) 0.5 part by mass), and 200 parts by mass of fused silica (SC-4053SQ, manufactured by addlex Corporation) were mixed and diluted with methyl ethyl ketone to obtain a varnish. The varnish was impregnated into an E glass woven fabric (thickness: 95 μm, mass (weight per unit area): 108g/m 2. or less) and dried at 130 ℃ for 3 minutes to obtain a prepreg containing a resin composition in an amount of 45 mass%.

(example 2)

10.0 parts by mass of the α -naphthol aralkyl type cyanate ester resin obtained in Synthesis example 1, 45.0 parts by mass of a novolak type maleimide compound (BMI-2300, manufactured by Dahe chemical Co., Ltd., functional group equivalent: 186g/eq.), 25.0 parts by mass of diallyl nanodiscmide (BANI-M, manufactured by Takayasu petrochemical Co., Ltd., functional group equivalent: 286g/eq.), 13.0 parts by mass of the compound represented by the above formula (22) obtained in Synthesis example 3, 6.9 parts by mass of a biphenyl aralkyl type epoxy compound (NC-3000H, manufactured by Nippon chemical Co., Ltd., functional group equivalent: 290g/eq.), 6.0 parts by mass of a silane coupling agent (Z-6040, Dow Corning Co., Ltd.), 6.9 parts by mass of a wetting dispersant (DISPERBYK-111, manufactured by Japan K Japan) and 1.0 part by YKK. and 1.0 part by mass of a wetting dispersant (DISK-161. YKK), BYK Japan KK) 1.0 part by mass, an imidazole curing accelerator (2,4, 5-triphenylimidazole (manufactured by tokyo chemical industry co.) 0.5 part by mass), and 200 parts by mass of fused silica (SC-4053SQ, manufactured by addlex Corporation) were mixed and diluted with methyl ethyl ketone to obtain a varnish. The varnish was applied by impregnation to an E glass woven fabric, and heated and dried at 130 ℃ for 3 minutes to obtain a prepreg containing 45 mass% of the resin composition.

Comparative example 1

10.0 parts by mass of the α -naphthol aralkyl type cyanate ester resin obtained in Synthesis example 1, 45.0 parts by mass of a novolak type maleimide compound (BMI-2300, manufactured by Daihuazai chemical Co., Ltd., functional group equivalent: 186g/eq.), 25.0 parts by mass of diallyl nadimide (BANI-M, manufactured by Takayasu petrochemical Co., Ltd., functional group equivalent: 286g/eq.) 5.0 parts by mass of diallyl bisphenol A (DABPA, manufactured by Daihuai chemical Co., Ltd., hydroxyl group equivalent: 154g/eq.) corresponding to the aromatic compound (A1), 7.5 parts by mass of a monofunctional epoxy compound (manufactured by ED-509E, manufactured by ADEKA Co., Ltd.) corresponding to a compound having an organic group having a valence of 1 represented by R, a biphenyl aralkyl type epoxy compound (NC-3000H, manufactured by Nippon chemical Co., Ltd.), and a mixture of a water and a water-based epoxy compound, Functional group equivalent: 290g/eq.)7.0 parts by mass, 6.9 parts by mass of a silane coupling agent (Z-6040, manufactured by Dow Corning Toray Co., Ltd.), 1.0 part by mass of a wetting dispersant (DISPERBYK-111, manufactured by BYK Japan KK), 1.0 part by mass of a wetting dispersant (DISPERBYK-161, manufactured by BYK Japan KK), 0.5 part by mass of an imidazole-based curing promoter (2,4, 5-triphenylimidazole (manufactured by Tokyo chemical Co., Ltd.)) and 200 parts by mass of fused silica (SC-4053SQ, manufactured by Admatox Corporation) were mixed and diluted with methyl ethyl ketone to obtain a varnish. The varnish was applied by impregnation to an E glass woven fabric, and heated and dried at 130 ℃ for 3 minutes to obtain a prepreg containing 45 mass% of the resin composition.

Comparative example 2

10.0 parts by mass of the α -naphthol aralkyl type cyanate ester resin obtained in Synthesis example 1, 47.0 parts by mass of a novolak type maleimide compound (BMI-2300, manufactured by Dahe chemical Co., Ltd., functional group equivalent: 186g/eq.), 36.0 parts by mass of bisallylnadimide (BANI-M, manufactured by Takayashi, Ltd., functional group equivalent: 286g/eq.) 7.0 parts by mass of a biphenyl aralkyl type epoxy compound (NC-3000H, manufactured by Nippon chemical Co., Ltd., functional group equivalent: 290g/eq.)7.0 parts by mass of a silane coupling agent (Z-6040, Dow Corning Toray Co., Ltd.), 6.9 parts by mass of a Ltd.), 1.0 part by mass of a wetting dispersant (DISRBYK-111, manufactured by BYK Japan) and 1.0 part by mass of a wetting dispersant (DISRBPEYK-161, manufactured by Japan) and 1.2 parts by mass of an imidazole accelerator (BYK-161, manufactured by Japan), 0.5 part by mass of 4, 5-triphenylimidazole (manufactured by Tokyo chemical industry Co., Ltd.) and 200 parts by mass of fused silica (SC-4053SQ, manufactured by Admatox Corporation) were mixed and diluted with methyl ethyl ketone to obtain a varnish. The varnish was applied by impregnation to an E glass woven fabric, and heated and dried at 130 ℃ for 3 minutes to obtain a prepreg containing 45 mass% of the resin composition.

[ production of Metal-clad laminate ]

A12 μm-thick electrolytic copper foil (3EC-III, manufactured by Mitsui Metal mining Co., Ltd.) was placed on top and bottom of 1 sheet of the prepreg obtained above, and laminated and molded at a pressure of 30kgf/cm2 and a temperature of 220 ℃ for 120 minutes to obtain a copper-clad laminate having an insulating layer thickness of 0.1 mm.

[ glass transition temperature (Tg) ]

After the copper-clad laminate was obtained as described above, the copper foil on both surfaces was removed therefrom by etching to obtain a sample. The dynamic viscoelasticity of the sample was measured in accordance with JIS K7244-3 (JIS C6481) using a dynamic viscoelasticity measuring apparatus (manufactured by TA Instruments Japan Inc.) under the conditions of a starting temperature of 50 ℃, an ending temperature of 350 ℃ and a temperature rising rate of 10 ℃/min. The maximum value of the loss elastic modulus (E') obtained at this time was taken as the glass transition temperature. The glass transition temperature is an index of heat resistance. In table 1, the value is described in the case where the glass transition temperature is in the region of 350 ℃ or lower, and the value is described in the case where the glass transition temperature is not in the region of 350 ℃ or lower, "> 350 ℃. The results are shown in Table 1.

[ formability of printed Circuit Board ]

After the copper-clad laminate was obtained as described above, the copper foil on both surfaces was removed therefrom by etching to obtain a sample. The surface of the sample was visually observed to evaluate the presence or absence of voids. When the presence of many voids was confirmed, the molding was impossible and the evaluation was "C", and when the presence of voids was confirmed but the number thereof was small, the molding was possible and the evaluation was "B"; if the presence of voids was not confirmed, the molding was considered to be satisfactory, and the evaluation was "a". The results are shown in Table 1.

[ minimum melt viscosity of prepreg ]

The minimum melt viscosity of the prepregs obtained in the examples and comparative examples was measured by using a rheometer (TA Instruments, Japan inc.) under conditions of a start temperature of 80 ℃, an end temperature of 180 ℃, a temperature rise rate of 3 ℃/min, a frequency of 10pts/s, and a strain of 0.1%. The lower the minimum melt viscosity, the better the flow characteristics (resin fluidity) at the time of producing the laminate sheet, and the more excellent the moldability. The results are shown in Table 1.

[ storage stability of prepreg ]

The prepreg obtained as described above was stored in a thermostatic bath at 40 ℃ for 1 week. The change in viscosity before and after storage was measured with a flow tester. Specifically, the measurement was carried out using a flow tester (manufactured by Shimadzu corporation) at a measurement temperature of 120 ℃, a tensile load of 10kg, and a die length of 10 mm. The smaller the change in viscosity, the longer the period during which the prepreg can be stored in a state in which the flow characteristics (resin fluidity) at the time of producing the laminate are good, which means that the prepreg storage stability is excellent. The results are shown in Table 1.

[ Table 1]

The present application is based on japanese patent application published on 26/5/2017 (japanese application 2017-104096), the content of which is incorporated herein by reference.

Industrial applicability

The present invention can provide a resin composition and the like having excellent moldability into a printed circuit board and excellent storage stability of a prepreg, and therefore, the present invention is applicable to the fields of printed circuit boards and the like used for semiconductor plastic packages.

Claims

1. A resin composition comprising an aromatic compound (A) and a maleimide compound (B), wherein the aromatic compound (A) is formed by directly bonding a 1-valent substituent represented by the following formula (1a) and a 1-valent substituent represented by the following formula (1B) to an aromatic ring,

CH＝CRCH- (1a)

RO- (1b)

In formula (1a), Ra represents a hydrogen atom or a 1-valent organic group, and in formula (1b), Rb represents a 1-valent organic group.

2. The resin composition according to claim 1, wherein in the aromatic compound (a), a carbon atom in the aromatic ring to which the 1-valent substituent represented by the formula (1a) is bonded and a carbon atom in the aromatic ring to which the 1-valent substituent represented by the formula (1b) is bonded are adjacent to each other.

3. The resin composition according to claim 1 or 2, wherein the 1-valent substituent represented by the formula (1b) is any 1-valent substituent represented by the following formulae (2), (3) and (4),

In the formulae (2), (3) and (4), R1 represents an optionally substituted, straight-chain or branched alkyl group or aryl group having 1 or more carbon atoms.

4. The resin composition according to claim 3, wherein R1 is a substituent represented by the following formula (5),

In formula (5), R2 represents a hydrogen atom or a 1-valent organic group.

5. The resin composition according to any one of claims 1 to 4, wherein the aromatic compound (A) comprises a compound represented by the following formula (6),

In the formula (6), 2R 3 each independently represents a hydroxyl group or an optional substituent represented by the following formulae (2), (3) and (4), and at least one of them represents an optional substituent represented by the following formulae (2), (3) and (4), R4 represents a single bond, an alkylene group, a phenylene group, a biphenylene group or a naphthylene group, R5 each independently represents a hydrogen atom, an alkyl group, a phenyl group, a biphenyl group or a naphthyl group,

6. The resin composition according to any one of claims 1 to 5, wherein the maleimide compound (B) is at least 1 selected from the group consisting of bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, polytetrahydrofuran-bis (4-maleimidobenzoate), and a maleimide compound represented by the following formula (7),

In the formula (7), R6 each independently represents a hydrogen atom or a methyl group, and n1 represents an integer of 1 or more.

7. The resin composition according to any one of claims 1 to 6, further comprising at least 1 selected from the group consisting of an epoxy resin, a cyanate ester compound, and an alkenyl-substituted nadimide.

8. The resin composition according to any one of claims 1 to 7, further comprising an inorganic filler (C).

9. The resin composition according to claim 8, wherein the inorganic filler (C) comprises at least 1 selected from the group consisting of silica, alumina, and boehmite.

10. The resin composition according to claim 8 or 9, wherein the content of the inorganic filler (C) is 30 to 500 parts by mass with respect to 100 parts by mass of the resin solid content.

11. a prepreg comprising: a base material, and the resin composition according to any one of claims 1 to 10 impregnated or coated on the base material.

12. A resin sheet comprising: a support and the resin composition according to any one of claims 1 to 10 applied to the support.

13. A laminated plate obtained by laminating 1 or more sheets of at least 1 kind selected from the group consisting of the prepreg according to claim 11 and the resin sheet according to claim 12, wherein the laminated plate contains a cured product of a resin composition contained in at least 1 kind selected from the group consisting of the prepreg and the resin sheet.

14. A metal-clad laminate comprising: at least 1 selected from the group consisting of the prepreg according to claim 11 and the resin sheet according to claim 12, and a metal foil disposed on one surface or both surfaces of at least 1 selected from the group consisting of the prepreg and the resin sheet, wherein the metal foil-clad laminate comprises a cured product of a resin composition contained in at least 1 selected from the group consisting of the prepreg and the resin sheet.

15. A printed circuit board, comprising: an insulating layer comprising the resin composition according to any one of claims 1 to 10, and a conductor layer formed on a surface of the insulating layer.

16. A method for producing a resin composition, comprising the steps of:

A step in which an aromatic compound (A1) in which a 1-valent substituent represented by the following formula (1a) and a phenolic hydroxyl group are directly bonded to an aromatic ring is reacted with a compound that reacts with the phenolic hydroxyl group to obtain an aromatic compound (A) in which a 1-valent substituent represented by the following formula (1a) and a 1-valent substituent represented by the following formula (1b) are directly bonded to an aromatic ring; and

A step of blending the aromatic compound (A) and the maleimide compound (B),

CH＝CRCH- (1a)

RO- (1b)